The effect of varying surfactant chain length (C-12, C-14, C-16, C-18) on the alkaline hydrolysis of the organophosphorus pesticide fenitrothion was determined for the following series of inert counterion cationic surfactants: dodecyltrimethylammonium bromide (DTABr), tetradecyltrimethylammonium bromide (TTABr), hexadecyltrimethylammonium bromide (CTABr), and octadecyltrimethylammonium bromide (OTABr). Plots of k(obs) versus [surfactant] at constant [KOH] showed saturation behavior at low total [Br-], and (constrained) S-shaped curvature was observed at high total [Br-]. k(obs) values increased with increasing surfactant chain length but decreased with added KBr. For systems exhibiting saturation behavior, further analysis of the results using the PPIE treatment as modified to account for HO-/Br- exchange allowed the evaluation of substrate binding constants, K-S, and micellar rate constants, k(2m). The binding constants increased with chain length (hydrophobicity), but ionic strength had no effect on K-S. Meanwhile, because of the increased K-S values as the surfactant chain length increased, the rate enhancements observed for fenitrothion degradation correspondingly increased. However, rate enhancements decreased with ionic strength because reactive counterions could not compete against the bromide anion for micellar binding sites. Low k(2m)/k(2w) ratios revealed that the observed rate enhancements were due to the so-called concentration effect rather than true catalysis. Finally, where the PPIE model failed (displaying S-shaped curvature), our results support the intervention of sphere-to-rod transitions that are favored at high ionic strength (> 0.01 M Br-) and lower temperatures as the cause of the S-shaped curvature.